Cationic surface active agents and method of preparation



Patented Nov. 13, 1951 cArIoNIc SURFACE ACTIVE AGENTS AND 1 ETnonorPREPARATION Jack T. Thurston; Riverside, Conn., and Wilbur N. Oldham,Monrovia, Califi, assignors to American Cyanamid Company,

New York,

N. Y., a corporation of Maine No Drawing.

Application February 4, 1947,

- 7 Serial No. 726,436

' 1 This invention relates wetting agents and methods for thepreparation thereof, and more particularly to the production of cationicsurface-active compositions which are valuable softening agents fortextiles.

This application is a continuation-in-part of our copending applicationSerial No. 542,246. filed June26, 1944, now abandoned. L.

In our earlier application, above identified, we described and claimedan improvedmethod for producing alkylol-substituted alkyl guanidinesalts by reacting an alkylene oxide of 2-4 carbon atoms with an alkylguanidine. The alkyl-substituted guanidine was preferably prepared byreacting the correspondingprimary or secondary amine with an aqueoussolution of cyanamide in the presence of an acidic material such ascarbon dioxide, acetic acid, hydrochloric acid and the like, thereaction preferably being carried out in the presence of an organicsolvent such .as ethanol, propanol, dioxane, acetone and the like.Underthese conditions a crude reaction mixture was obtained which couldbe condensed directly or after apreliminary concentration with ethyleneoxide, propylene oxide or other alkylene oxides.

The present application is directed particularly to the class ofproducts obtained by carrying out the above-described synthesis with theusev of carbon dioxide as the acidic material. We have found that theresults obtainable with carbon dioxide are entirely different from thoseobtained when acetic acid, hydrochloric acid or other acidic materialsare used in the above-described product. This difference is due to thefact that carbon dioxide, when reacted with a primary or secondaryaliphatic amine in water or an organic solvent, forms an amine salt ofan N-aliphatic carbamic acid by the following reaction:

sponding monoor di-substituted guanidinium salts by the reaction:

- It will be understood that in the above Equations land 2 the symbol R1represents an ali-v phatic radical, which may be either saturated orunsaturated, while the symbol R2 means either hydrogen (in the case of aprimary amine) .or a

second aliphatic radical which may be the same or different from R1, -;v

to surface-active or molecular. weight.

9 Qlaims'.i-(Cl.2 501) 1 2 The fact that an alkyl guam'dinium N-alkylcarbamate is formed, in accordance with the re-" actions outlined above,is demonstrated quanti tatively by the following procedure: A solutionor 134 grams (0.5 mol) of octadecylamine in 250' cc. of isopropanol isprepared in a flask equipped" with'a reflux condenser, thermometer andan inlet funnel by heating to 40 C. 12 grams of carbon dioxide gas arethen introduced, after which the temperature is raised to approximatelyC. and 140 cc. of a 22.5% aqueous solution'of cyanamide (0.75 mol) isslowly added with con-' tinuous stirring during an interval of 2.5hours. Additional carbon dioxide is passed into the solu tioncontinuously during the addition of the 031-- anamide solution and thenfor 15 minutes longer,

Per Cent Per Cent Per Cent Calculated for C H I N Octadecyl guanidinebicarbonate M (CgoHnNzOs 64. 4 11. 5 11. 3 Octadecyl guanidiniumN-octadecyl carbamate (O35Hs0N402) p 73. l 12. 8 M 8. 9 Found byanalysis 72. 96 13. 03 8.85 73. 18 12. 79 8. 81

Another compound was prepared from octylamine-in order to show that thesame reaction takes place withamines of substantially lower A suspensionof. 129 grams (1 mol) of n-octylamine was prepared in 200 cc. of waterat 50? C. and.22 grams of carbon dioxide were introduced. A 17.5%aqueous solution of cyanamide was then added in an amount of .360 grams(1.5 mols) over a 3-hour period at a temperature of 85-90 C. with"continuous stirring while continuingtheintroductlon of carbondiox; ide'during-the reaction and for one-half hour after all of the cyanamide hadbeen added.--0n cooling the reaction mixture a solid separated which wasfiltered off and air-dried. The solid weighed 182 grams and melted at104"-112". C.

with decomposition- A It A A sample was dissolved in hot ethanol,treated with an absorptive carbon black, filtered and allowed tocrystallize. This product was then recrystallized twice more fromethanol in order to obtain asample having a constant melting point of116-l20 .,C.1which did not change upon fur.-

ther recrystallization. Upon analysis of the dried sample for carbon,hydrogen and nitrogen the fol v lowing results were obtained:

positions of good wetting and textile-softening properties, andtherefore the preferred amines are those of 8-18-or-more carbon atoms.Typical compounds of this class are mono-n-octylamine,

Per Cent Per Cent Per Cent Calculated Ior- C- k H N Octyl guanidinebicarbonate (CwHzsNaOa) 61. 5 9. 9 18. 0 Octyl guanidinium N-octylcarbamate (C sH4oN4O2) 62. 79 11. 72 Found in sample prepared as de- M Yscribed above 62. 74 11.79 16. 53

In carrying out reactibns 1 and. 2 under the conditions describedjinthespecific"e xampl'es of our above-"entitled application, and particularlyunder the conditions described inExamples l and 2 thereof, wherein anexcess of cyanamide is used, the yield of guanidinium carbamateof'the'for mula'shown in Equation 2 is on the order of 90 '-'100%. Forsomeipurposes, however, and particularly for use in the preparation of acationic softening composition'fo r'textiles by admixture with anionicsurfaceactive agents containing a single long aliphatic'radical of atleast 12 carbonatoms, as' described in the copending application of E.A. Vitalis'et al.,Seria1 No. 593,758, filed May 14, 1945, now Patent No.2,427,242, a product containing jonlyfabout 50-70% of the amine in theformof aguanidinium carbamate is desired. Such a product can'easily beobtained by reducing the quantity ofcyana mide added to the reaction.

I Experience has shown that the products obtained by reactingthealiphatic guanidinium N aliphatic carbamateswith'an'alkylene oxide suchas "ethylene oxide, propylene oxide or butylene oxide are better"cationic wetting agents and softeners for textiles 7 than on thoseobtained by re' acting the. same allgylen oxides with guanidinium saltsof any other'acidfincludin' g the acetic acid, hydrochloric acid andother acidsdescribed in our above-entitled application. Accordingly, thecompositions of the present invention are those in which a compositioncontaining "an aliphatic guanidim'um'N aliphatic carbamate of theformula RiRzN-COOHRrRzNC (:N H) NHz in which R1" is an aliphaticradicalgpreferably of 8'to l8 orpmore carbon atoms and R2 is hydrogen ora similar aliphatic radical is reacted with an alkylene oxide containinga single epoxy group, i. e., the reaction products of ethylene oxide(CHzCI-IzO), propylene oxide. (CHaCH'CHaO) or. 'butylene oxidev(CH3.CH2.CH.CH2.O) .or .simie lar compounds such as glycidol. Whencomposi-. tions of good wetting and textilesoftening properties aredesired, all the aliphatic radicals of these compounds preferablycontain at least 8 carbon atoms, and. even better'results are obtainedwhen they contain about 12-.18Lcarbon atoms.

i The formation of. imonoand. di-aliphatic guanidine derivatives: fromthe corresponding mono-- and di-aliphatic amines by reacting the carbondioxide derivative thereof with cyanamide is described in ouricope'ndingapplication Serial No. 726,438, filed February 4, 1947. Any monoordi-alkyl amine'may be used .for this purpose including amines of lowmolecular weight such. as

mono 2 ethylhexylamine, mono n decylamine, monoln -.dodecylamine, mono ntetradecylamine, mono-n-hexadecylamine, monon-octadecylamine andmixtures thereof, all of which are readily obtainable from thecorrespondingmondcarboxylic acids. The corresponding di-alkyl aminessuch as di-n-octylamine (CtI-ImzNH, di-decylamin, di-dodecylamine, di-

tetradecylamine, di-hexadecylamine, and dioctad'ecylamine mayalsobeused. For, many purposes a mixtureof saturated and unsaturatedmono-alkyl amines of .16418, carbon atomsis par: ticularly.suitab1e...because..it is, availablegcommercially in largequantities.Thus,,for. exam; ple, a mixturecontaining about 25-30%, ofhexadecylamine, about. 25%... of. saturated octadecylamine, and about45-50%. of .unsaturated primaryv amines of 18 .carbon atoms, isavailable ,commercially. at arelatively. lowv price.

Any of the above worother primary or secondaryv amines may. bereacted.with, carbon dioxide, in water or an. organicsolvent such, aswethanol,propanol,.butanol,'. dioxane, or. acetone to. form the corresponding...-.mono or di-aliphatic carbamic acid-.amine. 'sa1t,, which can ,be.converted into. thefcorresponding mono: or di-.aliphatic-substituted.guanidinium, Nr-mono- 0. di-aliphatic. carbamate.by. reaction with cyanamide. Upon. condensing these guanidiniumcompounds. with .lower alkylene; oxides 0f, 2+ 4. carbon atoms thecondensation products. of the, present invention areobtained.

The amountof alkylene oxideicondensed in our product depends upon.. thedesired 7 property. or

properties and the degree and combinationof these properties in the useto. which .the pro ducts are put. General1yitis preferable. to. condensefrom 1-25.mo1s.of .a'lkyleneoxid'e foreach, mol of amine used.althoughlas. muc:h..asj1a-50v mols or. moremay becondens'edwhendesired. When water solubilitya-ndlwetting powerof the alkylene oxidecondensation'pr'oductare the desired properties, the amountlof alkyleneoxide condensed depends. largely. upon.,the..type; of the amineand theparticular.alkylenehoxideused .as well as the ratio of the alkyleneoxideltotheamine, It should be understood .that the condensation.withalkylene oxide introduces .wateresolubilizing. or hydrophilic groupsinto, thefinal condensation product whereas th'e radical or iadicals'"in the aliphatic amine is or;,are,,,hydrophobic or oil-solubilizinggroups. Theformation of compounds capableof orientating themselves at,an toil-water interface to produce surface activityqandwetting anddetergent propertiestakes place by. combining enough ail yle e x j Jiiih'thefchos en aliphatic amineto produce a'b'ala'nce' between thehydrophilic and hydrophobic ioups. Underthese circumstances'preferablyjll2 mols and when.de sirable as much as.1-50 or more molsofalkylene oxide can be condensed for each mol of amine used. Thus,forexampl'e, whenoctadecyl amine is used we havefoundithatoptim-umWetting and emulsifying properties areobtainediibyhcondens-r garne ing about 6-12 mols ofethylene 'oxide foreach mol of this amine. With dodecyl amine, on the other hand,a-molar-ratio of about 3-6 mols of ethylene oxide for each mol of theamine'produces a condensation product having good wetting properties.With alkyl amines of lower molecular weight, such as mono-octyl amine,1-2 mols of ethylene oxide are-in many cases-sufficient to impart therequisite degree of water-solubility to the composition. Largerquantities of alkylene oxide can of course be used as stated above.

The condensation productsobtained by the process of our invention varyin form from waxes to viscous liquids depending on the type of amineemployed and the type and molecular amount of alkylene oxide condensedtherewith. As stated above, the degree of water-solubility dependslargely on the amount and type of alkylene oxide used in thecondensation.

Essentially our process comprises reacting carbon dioxide with asubstituted amine having at least one hydrogen atom attached to theamine nitrogen atom, preferably. 'a primary or secondary aliphatic aminein which each aliphatic radical contains 8-18 or more carbon atoms,reacting cyanamide withthe product therefrom and then introducing analkylene oxide containing 2-4 carbon atoms until a water-soluble productis obtained. The amount of alkylene oxide to be used depends on thedegree of water solubility and other properties that may be desired, asis explained above.

The reaction of the carbon dioxide with the amine is carried out byforming a solution of the amine and then bubbling preferably an excessof carbon dioxide through the solution for a suflicient length of timeto complete the reaction. The cyanamide is then introduced into the saltcompositions can be obtained by the process 7 of our invention forreaction with ethylene oxide which contain about 50-70 mol per cent ofthe amine in the form of aliphatic guanidinium N- aliphatic carbamate.and about 50-30 mol per cent in the form of the. aliphatic amine salt ofan N-aliphatic carbamic acid. This corresponds to a reaction product ofcyanamide with the aliphatic amine salt of N-aliphatic carbamic acidwhich contains about -25. mol per cent of the.

amine in an unconverted condition; i. e., present as a salt of thecarbamic acid, about 50 mol per cent of N-aliphatic-substituted carbamicacid, and about 25-35 mol per cent of aliphatic-substituted guanidine,based on the total quantity of amine used. Such a composition may beobtained by adding to" the reaction mixture an amount of cyanamide lessthan that theoretically into a'water sol'uble condition by reactiontherewith. I

In carrying out complex'organic reactions with reagents such as used inthe process of this application it is tobe expected by one skilled inthe artthat considerable quantities of by-prodnets are formed and thatreproducible results would be difficult to obtain. We have found, and itis one of the principal advantages of our invention, that our processgives reproducible results and it is relatively easy to obtain uniformquality from batch to batch in large-scale production.

Another important advantage of our process is its flexibility in thatany desired quantity of alkylene oxide may be condensed with the productafter the cyanamide reaction. Where desirable as much as from 8-12 molsof the oxide can be condensed for each mol of amine used. This isa veryuseful advantage in the preparation of wettingagents for it is a simplematter to obtain any desired balance between the quantity of hydrophilicand hydrophobic groups present in the final products.

. Still another and perhaps the most important advantage of ourinvention is that by reacting carbon dioxide with an amine, reactingcyanamide with the reaction products therefrom and then condensing analkylene oxide therewith, a new and improved class of compositions areproduced which are useful as cationic surface active agents.

The invention will be illustrated in greater detail by the followingspecific examples. It should be understood, however, that while theseexamples vmay describe some of the more specific features of theinvention, they are given primarily for purposes of illustration and theinvention in its broader aspects is not limited thereto.

Example 1 A surface active agent in which about 1.5 moles of cyanamideand about 6 moles of ethylene oxide were used for each mole ofoctadecylamine was prepared as follows:

The octadecylamine was added to the alcohol and water contained in a20-gallon, glass-lined kettle and heated to approximately 60-65" C. inorder to obtain a complete solution. Carbon dioxide was then passed intothis solution for approximately one hour. The temperature was then,raised to approximately C. and the cyanamide solution added to thewell-stirred mixture during an interval of 4-4.5 hours. Carbon dioxidewas also passed into the solution continuously during the addition ofthe cyanamide solution and then for another hour, during which time thetemperature was maintained at 80 C.

' A product in the amount of 112 lbs. was obtained which was calculatedas having 47% solids. 100 lbs. of acetone was added to this productwhich was then placed in an autoclave provided with internal coils fortemperature regulation. The autoclave temperature was raised to and heldat C. and ethylene oxide was passed in at such a rate that the pressurewas at all times less than 75 lbs. per square inch. A total of 37.5

lbs'of ethylene oxide was combined with the product'in this manner.

hi eistfll ihqta conc ntra t so ids-con: tent of approximately 87.5% bydistillation. Whemthe:z st lati n. emp r t r r a 1 0., a inch vacuum wasapplied and the heating continued until the boiling temperature at thereduced pressurewas 95? C. The yield was 10Q.5. lbs. .of ;a productcontaining 85.7 72; solids.

Emample ,7 2

A .secondbatch of. product :waswpreparedinwhichqisopropyl alcoholwas,used as solventand about .8 moles of ethylene oxide was, used for each:mole of. octadecylamine. The materials employed were asfollows 1 Lbs-Octadecylamine "83; Y Isopropyl alcohol 41.5 Carbon dioxide .(theory,6.5 lbs.) "27.5 Wateim 5.28, Cyanamide (23.9% aqueous solution) 79.5Ethylene oxide 110 The amine was dissolved in the isopropyl al-.- coholby heating to 45 C., and then thesolution was pumped into a 50-gallonenameled kettle along with the water. During 1.5 hours. 19 lbs. of Dry-Ice was, added in small portions, thetemperature being kept below 65 C.by coolin The reaction was not apparently exothermic after one half ofthe Dry Icehad been added.

The cyanamide solution wasnext added slowly 10-12 lbs. cou1d .be addedduring /2; hour and still maintain. the pressure below 20; lbs. persquare inch. It was noted that-when the ethylene oxide addition'wasstopped; the pressure dropped abruptly, indicating almost instantane-g-Qua-reaction. After the addition was complete the-product was heated to90 C. for afew minutes, then cooled to 70 C. and allowed to.

Example 3 The procedure described in Example 1 was.

carried out using various amines as starting material. The indicatedamount .of the aliphatic guanidinium N-aliphatic carbamate compositionobtained after the cyanamide .addition was reacted with the quantitiesof ethylene oxide listed in each case .to obtain the product describedin the following table. In all cases the ethylene oxide condensation wascarried out at 125? C. during 1 hour.

Substituted .Eghylfne, ARpprim,

guaniin e a 0 dinium Amine Used gigs; ig Amine to Characteristics. ofProduct carb amate I 'Ethylene grams g mol Oxide i 72 Dicthyl Amine;0.413 300 i 18 0. 41 1:1 Water solubleyvery basic. 76 Butylaminc.. 0.436325' 28 0.637 1:1.5 I Do: 129 Dmiecylaniine.v 0.447 550 19 0. 433 1:1,Soluble in dilute acetic acid;

I foams well. I 129 do 0.447. 550 79 1.8 7 1:4 Water soluble; basic.

over a period of 4.75 hours under arefiux con- Example 4 denser, thereaction temperature being kept at 83.89 C. by heating. Simultaneously,a total of 8.5 pounds. of carbon .doxide was bubbled through thereaction mixture to make certain Cationic surface-active compositionswere prepared with octadecylamine using the procedure described inExample 1. The material and the that an excess was present at all times.After quantities are tabulated below:

Oyanamide Cyanemidc: Octadecyl, amine, Isopro 'Water,. Molar Per Cent 1g. moles: panel, g. 1 Ratio Amine g. n g.. moles Conversion 200 I 0. 72"100 10 w 76 0. 36 .5 72.0 400 1.44, 200 Y 20.x 88:5 0. 432 .3 49.0 5202. 0 t 260 10' -22() 0.82 .41 68.4 520 2. Q 255 10 193' 0. 72 37 67. 6

:To octadecyl guanidinlum'N-octadecyl carbamace in reaction produc thecyanamideaddition-was complete the mixture Upon reaction with 5-7 molsof ethylene oxide for washeated an additional hour.-

The kettle wasadapted for pressure :and an ethylene oxide tankattachedeso that ethylene oxide could be introduced into the kettleabove the surface of the reaction. mixture. The ethylene oxide wasslowlyaddedat 60-66 C., and the reaction was found to, be moderatelyexothermic so that almost continuous cooling was necessary. The ethyleneoxide;was added at-such a rate that at 60-66 C. the internal pressure inthe kettle did not exceed 20 -lbs. per square inch..

A total of 110 lbs of ethylene oxide was added during incurs. Duringthefirst hour period it was possible to add 19 -lbs-. of ethylene oxide,but. towardv the endof the addition periodonly each mol ofoctadecylamine used-as starting mae terials water-soluble products wereobtained which were particularly well suited for use in the preparationof cationic softeners for textiles.

Example 5 quan ties u edri pr p azt se. surfa e.

active agents. are tabulated in the iollowing table: i

Ethylene Run Ox de I A Num- Solvent Isolation Procedure ber Molar Ratio1 .22 2 Dioxane 1000 cc. Eggiorated to wt. of gr.

2 17 1.6 Dioxane 300 cc Evaporated to thick syrup. 3 17 1.6Acetone500cc... Carbonated M. P.,

' Gil-65 C. .4 11 1 Acetone 500 cc Evaporated to thick Y sy up;

Example 6 To 50 g. of product after the cyanamide addi tion according tothe procedure of Example 1 was added 47.5 g. (0.84 mol) propylene oxide(amine to ethylene oxide ratio .6 to.1 )-andthe mixture was heated in apressure bottle for 15 hours at 65 C. Evaporation of the solvent underreduced pressure left' 100 g. of a thick liquid that slowly depositedsolid on standing.

The amine and alcohol were placed in a 1 liter three-necked flaskequipped with a reflux condenser, thermometer and an inlet funnel. 25grams of carbon dioxide were bubbled through the solution which was atroom temperature. The temperature was then raised to approximately 80 C.and the cyanamide solution was added to the well stirred mixture duringan interval of 2.5 hours. Carbon dioxide was also passed into thesolution continuously during the addition of the cyanamide solutionandthen for another 15 minutes.

660 grams of ethylene oxide (15 mols of oxide for each mol of amineused) were passed into the flask over a period of 20 hours during whichtime the temperature of the reaction mixture was between 65-75 C. Thismixture was then divided into two equal parts. One of these wasconcentrated to a solids content of about 87% to yield 504 grams of aproduct which had the appearance of a yellow syrup.

Additional ethylene oxide was added to the remaining half of the dividedsample during which addition the temperature of the reaction mixture wasalso between 65-"I5 C. The ethylene oxide addition was continued until330 grams (7.5 mols) were added and this quantity together with that ofthe first addition amounted to a total of 30 mols of oxide condensed foreach mol of amine used. The mixture after this second ethylene oxideaddition was concentrated to a solids content of about 87% to yield 880grams of a yellow syrup-like product. Both products were water solubleand showed good cationic surface activity.

- Example 8 "A sample was prepared as follows:

Mol. Wt. Amt. Mols.

Octadecylamine 26l 134. Carbon dioxide 44 in excess cyanamide (22.5%aqueous solution); 42 140 cc. 0. Isopropyl alcohol I 250 cc.

The amine and alcohol were placed in a 1 liter three-necked flaskequipped with a reflux condenser and an inlet funnel. Upon heating to atemperature of 40 C: the amine dissolved. The temperature was thenraised to approximately C. and the cyanamide solution was added to thewell stirred mixture during an interval of 2.5 hours. Carbon dioxide wasalso passed into the solution continuously during the addition of thecyanamide solution and then for 15 minutes more.

550 grams (12.5 mols) of ethylene oxide which amounted to 25 mols ofoxide for each mol of amine used Were then passed into the flaskover aperiod of 20 hours and during this addition the temperature of thereaction mixture was between 65-'75 C. The mixture was divided into twoequalparts. One of these was concentrated to a solids content of about72% to yield 505 grams of product.

The addition'of ethylene oxide was continued with the remaininghalf ofthe divided sample until an additional 275 grams (6.75 mols) were added.Thus the total ethylene oxide addition for this half of the sampleamountedto 50 mol of of the reaction mixture wasalso between 65 -75" C:After adding the additional amount of the oxide, the reaction mixturewas concentrated to a solids content of about 82% to yield 778 grams ofproduct. Both products were water soluble and showed good cationicsurface activity.

A considerably cheaper product of approximately the same molecularcomposition and having equally good cationic surface activity i obtainedby substituting commercial mixtures of higher aliphatic amines for theoctadecylamine used in the above examples. Thus, for example, a mixturecontaining about 25% of hexadecyl amine, 25% of octadecyl amine, and 50%of octadecenylamine is available commercially in large quantities, andis a preferred raw material in practicing the present invention.

What we claim is:

1. An alkylol-substituted aliphatic guanidinium N-alkylol aliphaticcarbamate, said carbamate being prepared by reacting an aliphatic aminehaving at least one hydrogen atom attached to the amine nitrogen atomwith suflicient carbon dioxide to form a salt therewith, reacting theamine salt so obtained with cyanamide to convert a portion of the aminesalt to the corresponding aliphatic guanidine salt, and condensing theresulting product with an alkylene oxide of 2-4 carbon atoms.

2. A surface active agent prepared by reacting carbon dioxide with analkylamine of 8-18 carbon atoms and having at least one hydrogen atomattached to an amine nitrogen atom, reacting cyanamide with the producttherefrom and then introducing an alkylene oxide having 2-4 carbon atomsuntil 1-12 mols of the oxide have condensed for each mol of amine used.

f'ing an alkylene oxide having 2-4 carbon atoms -until 1-12,mo1s of theoxide have condensed for xeachniolof amine used.

4; -A surface active-agent'- prepared by reacting carbon dioxide withoctadecyl amine, then reacting cyanamide with the products therefrom andiather'eafter introducing}; ethylene: oxide until' 1-12 -:mo1s:of:saidoxide :have: condensed .for. each mol ;szofssaidamineiused.

""15. Ascation-icazsurfaceeactive composition coniatainingoasfsa:p'rincipal constituent. an alkylolz-ssuhstituted aliphaticg-uanidiniumN-alkylol-subaz stitutedz aliphatic carb amate pr ep ared by; reacting tcarbontdioxide with:anwaliphatic-zamine of 8-18 tecarbon' atoms andhaving: at least, 1 hydrogen Tiatom attachedzto ritheramine: nitrogen 1atom, re

acting cyanamide with the products therefrom, iiandithen-condensingtherewith an alkylene oxide fihaving 2-4:carbon atoms.

6. Z'Ai cationic-surface active composition containing: as a principalconstituent an alkyl-alkylol 7.1 In :the rmanufacture :of'xacationicsu'rface- :a'ctive agent: thermethod' ofiproducing a mixturerot-aliphatic :guanidinium N ..a1iphatic' "carbamate andaali-phaticamineisalt-ofN-aiiphatic carbamic E12 leacidswhichrcomprisesreactinganaliphaticzamine salt of N-aliphatic carbamic acid of the form'ifia inwhich R is an aliphatic radicaLofL8-18 carbon atoms with a quantity. ofcyanamide less than that necessary to convert all of the aliphatic aminesalt to the corresponding guanidinium salt. 8.-A method according toclaim 7-in-whichthe quantityof cyanamidecis'within the rangeof 0.3

vmolto 0.6 .mol for. eachmolof the N-aliphatic carbamic acid salt.

9. A method ofproducing acationic surfaceactive agent whichcomprisesl'carrying 'outthe '1 25 -guanidinium N alkyra'lk'ylolcarbamate prepared 1 method defined byclaim 8 and condensing theproductwith ethylene'oxidein' the ratioof about 1-12 mols of ethyleneoxide for each mol of aliphatic amine.

JACK T. THURSTON. WILBUR N. OLDHAM.

jL-REFERENCES CITED "The"io'11owing references are of record in thefilebf'this" patent:

OTHER REFERENCES Flascheutrager et a1., Chem. Abstracts, vol; .25, VD.497 (1931).

Certificate of Correction Patent No. 2,574,510

November 13, 1951 JACK T. THURSTON ET AL.

d be read as corrected above, so that the e record of the case in thePatent Oflice. Signed and sealed this 26th (1 ay of February, A. D.1952.

THOMAS F. MURPHY,

Auu'akmt 0m of Patentc.

1. AN ALKYLOL-SUBSTITUTED ALIPHATIC GUANIDINIUM N-ALKYLOL ALIPHATICCARBAMATE, SAID CARBAMATE BEING PREPARED BY REACTING AN ALIPHATIC AMINEHAVING AT LEAST ONE HYDROGEN ATOM ATTACHED TO THE AMINE NITROGEN ATOMWITH SUFFICIENT CARBON DIOXIDE TO FORM A SALT THEREWITH, REACTING THEAMINE SALT SO OBTAINED WITH CYANAMIDE TO CONVERT A PORTION OF THE AMINESALT TO THE CORRESPONDING ALIPHATIC GUANIDINE SALT, AND CONDENSING THERESULTING PRODUCT WITH AN ALKYLENE OXIDE OF 2-4 CARBON ATOMS.